JPH03137228A - Dope dyed yarn for fishing net and fishing net - Google Patents

Abstract

PURPOSE:To obtain a dope dyed yarn for fishing net having excellent resistance to decomposition with amine, high modulus and high specific gravity comprising core component of specific a polyester containing colorant and sheath component of a polyamide. CONSTITUTION:The objective dope dyed yarn is composed of core-sheath type conjugate fiber comprising (A) core component of a polyester containing polyethylene terephthalate as principal ingredient and (B) sheath component of a polyamide. In said fiber, content of the component A is 30-90wt.% and colorant is contained in the component A in an amount of 0.1-5wt.% to the component A. Furthermore, said fiber has >=0.8 intrinsic viscosity [eta] 160X10<-3>-190X10<-3> birefringence and >=1.380g/cm<3> density of the polyester in the component A and >=2.8 relative viscosity in sulfuric acid [etar], >=45X10<-3> birefringence and >=1.135g/cm<3> of the component B.

Description

[Detailed description of the invention] [Industrial application field] TECHNICAL FIELD The present invention relates to spun-dyed yarn for fishing nets and fishing nets.

More specifically, it is a spun-dyed yarn for fishing nets that has excellent resistance to amine decomposition against ammonia, etc. generated by the corrosive decomposition of fish and shellfish, and has a high modulus and high specific gravity, and spun-dyed yarns using the spun-dyed yarn for fishing nets. It concerns fishing nets.

[Conventional technology]

Traditionally, polyamide fibers and polyester fibers have been mainly used for fishing nets, and polyester has the characteristics of high specific gravity and high tensile strength underwater.
Especially recently, a considerable amount of fabrics have been replaced with polyester.

However, when used for fishing nets, the raw yarn goes through a twisting process and is knitted into knotted nets, knotless nets, raschel nets, etc., and then dyed in a dyeing process, but this dyeing process is expensive. The amount of residual dye is also high, and there are many problems from the viewpoint of preventing environmental pollution. Therefore, in recent years, there has been a strong tendency to want to eliminate this process, and the dyeing process has been omitted using dyed polymers in order to streamline the dyeing process and prevent pollution. Regarding colored yarn, JP-A-57-7
No. 7318, Japanese Patent Publication No. 1-35089, etc. are disclosed.

[Problem to be solved by the invention]

Polyamide fibers used as yarn for fishing nets have excellent durability and resistance to amine decomposition, but have the disadvantage of low specific gravity and difficulty sinking.

Also, because the modulus is low, there is a drawback that the fishing net sways greatly due to waves, ocean currents, etc.

On the other hand, polyester fibers have a high modulus and a high specific gravity, which solves the problems of fishing nets using polyamide fibers, but the problem is that they have poor amine decomposition resistance and cannot withstand long-term use. was there. That is,
After fishing nets are used, they are dried on the beach, but during this process, the seafood still attached to the nets rots and generates ammonia, and especially when exposed to high temperatures from sunlight, fishing nets made of polyester fibers decompose into amines. The strength of the fabric is significantly reduced. Therefore, fishing nets made of polyester fibers are strongly required to have improved resistance to amine decomposition.

Also, the above-mentioned Japanese Unexamined Patent Publication No. 57-77318, Japanese Patent Publication No. 1
In the case of spun-dyed yarns such as those disclosed in Publication No. 35089, they can exhibit a "color tone" and "gloss" similar to those of dyed products, but there is a problem that the strength decreases due to the addition of colorants, and in addition, the polyamide fibers and polyester fibers described above The shortcomings of each have not been resolved.

An object of the present invention is to solve the problems of the prior art described above, and to provide a dyed yarn for fishing nets that has excellent amine decomposition resistance, high modulus, and high specific gravity.

Another object of the present invention is to use the dyed yarn for fishing nets,
An object of the present invention is to provide a spun-dyed fishing net that has excellent amine decomposition resistance, high modulus, and high specific gravity.

[Means and effects for solving the problems] The present invention has the following features: (1) A spun-dyed yarn for fishing nets and fishing nets made of composite fibers, the composite fibers having a core component of polyester containing ethylene terephthalate as a main component. It is a core-sheath type composite fiber having polyamide as a sheath component, the proportion of the polyester core component is 30 to 90% by weight, and the coloring agent in the polyester core component is 0.1 to 5.0% by weight relative to the polyester. %, and the intrinsic viscosity of the polyester core component [η
] is 0.8 or more, birefringence is 160X10-8 to 190X
10-", the density is 1.380 g/cm" or more, and the sulfuric acid relative viscosity [ηr] of the polyamide sheath component is 2.8 or more,
Birefringence is 45X10-” or more, density is 1.135g/c
m” or more, and (2) the spun-dyed yarn for fishing nets described in (1) above has a strength of 5.5 g/d or more and an elongation of 20% or more, initial tensile resistance 60 g/d or more, density 1.200 g
/cm” or more, dry heat shrinkage rate is 7% or more, wet knot strength is 4
．． (3) A fishing net characterized by using the dyed yarn for fishing nets described in (1) above, (4) The above-mentioned A fishing net characterized by using the dyed yarn for fishing nets described in (2).

The contents and effects of each element constituting the present invention will be explained in detail below.

The spun-dyed yarn for fishing nets according to the present invention and the fishing net obtained using the spun-dyed yarn for fishing nets cannot be obtained using spun-dyed yarns of conventionally used polyamide fibers and polyester fibers. It has high modulus properties close to that of polyester fibers, amine decomposition resistance close to that of polyamide fibers, and the strength of dyed yarn for fishing nets is 5.
5g/d or more, elongation 20% or more, density 1.200
g/cm3 or more, initial tensile resistance of 60 g/d or more, and wet knot strength of 4.5 g/d or more.

The above-mentioned characteristics of the dyed yarn for fishing nets according to the present invention are that it is made of a core-sheath type composite fiber whose core is polyester and whose sheath is polyamide, and the polyester and polyamide fiber portions forming the core and sheath of the composite fiber are specified. It is characterized by having certain physical properties. That is, the intrinsic viscosity [η] of the polyester forming the core component is 0.8 or more, and the birefringence is 160.
X10-8 to 190X10-8, density 1゜380g/
cma or more, the sulfuric acid relative viscosity [ηr] of the polyamide forming the sheath component is 2.8 or more, and the birefringence is 45X10-
2. Density is 1.135 g/cm or more.

The polyester which is the core component of the composite fiber of the spun-dyed fishing net yarn of the present invention and the fishing net obtained using the spun-dyed fishing net yarn of the present invention is preferably a polyester consisting essentially of polyethylene terephthalate units. The copolymer component may be contained to an extent that does not substantially reduce the physical and chemical properties of the polyethylene terephthalate polymer, for example, less than 10%.

The copolymerization components may include dicarboxylic acids such as isophthalic acid, naphthalene dicarboxylic acid, and diphenylcarboxylic acid, and diol components such as ethylene oxide, propylene glycol, and butylene glycol.

In order to obtain a strength of 5.5 g/d or more for the spun-dyed yarn for fishing nets according to the present invention, the intrinsic viscosity [η] of polyethylene terephthalate, which is the core component of the composite fiber for the spun-dyed yarn for fishing nets according to the present invention, is set to 0.
It is necessary to have a high viscosity of 7 or more, preferably 0.8 or more.

On the other hand, the polyamide which becomes the sheath component is polycapramide, polyhexamethylene adipamide, polytetramethylene adipamide, polyhexamethylene dodecamide, polyhexamethylene dodecamide, polyhexamethylene terephthalamide, polyhexamethylene isophthalamide. etc., and copolymers and blend polymers made of two or more of these are used, and polyhexamethylene adipamide is particularly preferred.

Similar to the polyester core component, the polyamide sheath component polymer also requires a high degree of polymerization in order to obtain high-strength spun-dyed yarn for fishing nets and fishing nets obtained using the spun-dyed yarn for fishing nets, and the relative viscosity of sulfuric acid is 2.8. It is preferably 3.0 or more.

The proportion of the polyester core component of the spun-dyed fishing net yarn of the present invention and the composite fiber of the fishing net obtained using the spun-dyed yarn for fishing nets is 30 to 90% by weight. Polyester core component is 3
If it is less than 0% by weight, it will not be possible to obtain a spun-dyed yarn for fishing nets that can effectively utilize the high modulus properties of the polyester component, and the density will be low, making it impossible to obtain preferred spun-dyed yarns for fishing nets and fishing nets.

On the other hand, if the polyester core component accounts for 90% by weight or more, the amine decomposition resistance of the polyamide sheath component cannot be fully expressed, and the polyester core component will undergo amine decomposition. can't get it.

The coloring agent added to the polyester core component is 0.1 to 5.0 wt% based on the polyester. If the amount of coloring agent added is less than 0.1 wt%, it will not be possible to obtain dyed yarn for fishing nets with sufficient "color tone" and "shine", and if the amount of coloring agent added exceeds 5.0 wt%, it will not be strong enough. There is a large decrease in the strength of fishing nets, making it impossible to obtain high-strength spun-dyed yarn for fishing nets and fishing nets.

As the coloring agent to be added to polyester, it is sufficient to use a coloring agent that is usually used for base dyeing, such as carbon black, an anthraquinone-based brown coloring agent, an anthraquinone-based purple coloring agent, a perinone-based red coloring agent, etc.
One or more types of colorants may be added.

In the spun-dyed yarn for fishing nets of the present invention and the composite fibers for fishing nets obtained using the spun-dyed yarn for fishing nets, both the polyester core component and the polyamide sheath component are highly oriented and crystallized, The birefringence of the polyester core component is
It is 160X10'-3 to 190X104. 160X
If it is less than 10-”, the strength of the composite fiber is 5.5 g/d or more,
The initial tensile resistance may not exceed 60 g/d, and on the other hand, if it exceeds 190 x 10-'', the bending fatigue resistance in water may deteriorate.

On the other hand, the birefringence of the polyamide sheath component is 45X1()-8 or more. If the birefringence is less than 45 x 10-'', it is difficult to obtain high-strength and high-modulus spun-dyed yarn for fishing nets and fishing nets, and it is also difficult to sufficiently exhibit amine decomposition resistance.

Furthermore, the density of the spun-dyed yarn for fishing nets of the present invention and the composite fibers for fishing nets obtained using the spun-dyed yarn for fishing nets is such that the density of the polyester core component is 1.380 g/em" or more, and the density of the polyamide sheath component is 1.135 g/em" or more. /cm” or more. If the density is not above the specified value, the density of the dyed yarn for fishing nets and the fishing net obtained using the dyed yarn for fishing nets will not have a high specific gravity of 1.200 g/cma or more, and the resistance in water will be poor. Bending fatigue resistance is not sufficiently improved, and it is also difficult to sufficiently exhibit amine decomposition resistance, making it impossible to obtain preferred spun-dyed fishing net yarns and fishing nets.

The dyed yarn for fishing nets according to the present invention characterized by the above has a high strength of 5.5 g/d or more, an initial tensile resistance of 60 g/d or more, and an elongation of 20% or more, and is preferable for fishing nets. A dyed yarn is obtained, and a fishing net using this dyed yarn for fishing nets is a high-strength fishing net.

Preferred embodiments for producing the spun-dyed fishing net yarn according to the present invention and the fishing net obtained using the spun-dyed fishing net yarn are as follows.

The spun-dyed yarn for fishing nets according to the present invention and the fishing net obtained using the spun-dyed yarn for fishing nets are made of composite fibers having a core of polyester and a sheath of polyamide. A polymer consisting essentially of polyethylene terephthalate with a viscosity [η] of 0.75 or more, usually on the 0°85 range, is used.

As the polyamide sheath component polymer, a high polymerization degree polymer having a sulfuric acid relative viscosity of 2.8 or more, usually 3.0 or more is used.

It is preferable to use two extruder type spinning machines for melt spinning the polymer. The polyester and polyamide polymers melted by each extruder are introduced into a composite spinning pack, and spun into a composite fiber with polyester in the core and polyamide in the sheath through a composite spinning nozzle.

The spinning speed is 500 m/min or more. Immediately below the spinneret, a heated atmosphere of 200° C. or higher, preferably 260° C. or higher is created over a distance of 5 cm or more and within 1 m by providing a heat insulating cylinder or a heating cylinder. After passing through the above-mentioned heating atmosphere, the spun yarn is quenched and solidified with cold air, and then an oil agent is applied thereto and taken off by a take-up roll that controls the spinning speed.

Control of the heating atmosphere directly below the spinneret is important in order to maintain stringiness during spinning, and is particularly important at high speeds. The taken-off undrawn yarn is usually drawn continuously without being wound up, but it can also be drawn in a separate step after being wound up. In order to understand the physical properties of the undrawn yarn before drawing, the birefringence of the undrawn yarn sampled after passing through a take-up roll was oriented to 5X10-8 or more in the polyamide sheath and 10XIO-'' or more in the polyester core. are doing.

If the spinning speed is less than 500 m/min, the durability of the core-sheath composite interface will be poor, and preferred spun-dyed yarn for fishing nets and fishing nets will not be obtained.

Next, the undrawn yarn is hot drawn at a temperature of 80°C or higher, preferably 120°C or higher. Stretching is performed in one stage or in multiple stages of two or more stages, and the total stretching ratio is 1.5 to 6.
5 times the range.

A fishing net is manufactured using the spun-dyed yarn for fishing nets made of composite fibers manufactured by the method described above. Although the structure of the fishing net may be any generally known structure, it is preferable that the dyed fishing net according to the present invention be manufactured and used as a fixed net or a purse net.

3--14 = The definitions and measurement methods regarding the fiber structure parameters and fiber physical properties according to the present invention are as follows, as will be explained below using examples.

Physical properties of polyester fibers (a) Birefringence: After dissolving the polyamide sheath component in formic acid, sulfuric acid, fluorinated alcohol, etc., the fibers were measured by the interference fringe method using a transmission quantitative interference microscope manufactured by Carl Zeiss Jena (East Germany). The average birefringence observed from the side was determined. Measurements were taken at 2μ intervals from the surface layer of the fiber toward the center, and the average value was determined.

(b) Density: The polyamide sheath component is dissolved and removed with formic acid, sulfuric acid, fluorinated alcohol, etc., and carbon tetrachloride is removed with heavy liquid, n-
25 using a density gradient tube prepared with hebutane as a light liquid.
Measured at °C.

(a) Birefringence of polyamide: As with the polyester core fiber, using a transmission quantitative interference microscope, only the surface layer polyamide fiber portion was measured from the side by the interference fringe method.

(b) Density: The density of the composite fiber was measured at 25°C using a density gradient tube made with carbon tetrachloride as a heavy liquid and n-heptane as a light liquid, and calculated from the density of the composite fiber and the density of the polyester core. I asked for it.

〔Example〕

Examples 1, 2) Comparative Examples 1 to 4 Intrinsic viscosity [η) 1.05, carboxyl end group concentration 10
, 5eq/10'H polyethylene terephthalate base chips and polyethylene terephthalate master chips containing the carbon black shown in the table are blended at a ratio of master chip/base chip = 1/33 (weight ratio). Hexamethylene adipamide (nylon 66, sulfuric acid relative viscosity ηr
3.3) were each melted using a 4oφ kustruder-type spinning machine, introduced into a composite spinning pack, and spun from a core/sheath composite spinneret into a black spun-dyed composite yarn with polyethylene terephthalate in the core and polyamide in the sheath. . The proportions of the core and sheath components were varied as shown in the table. The hole diameter of the cap is 1.2m.
mφ and 28 holes were used. Polyethylene terephthalate was melted at 295°C and polyhexamethylene adipamide was melted at 290°C, and the spinning back temperature was set at 300°C. A 15 cm heating cylinder was attached directly below the mouthpiece, and the atmosphere inside the cylinder was heated to 290°C. The ambient temperature is the ambient temperature measured at a position 10 cm below the mouth surface and 10° C. away from the outermost thread.

A uniflow chimney with a length of 100 cm is installed under the heating cylinder, and cold air at 20°C is blown at 30 m/s perpendicular to the yarn.
It was sprayed at a speed of 1 minute and cooled. The cooled and solidified yarn was oiled, the yarn speed was controlled by a take-up roll rotating at the speed shown in the table, and then the yarn was drawn continuously without being wound.

The film was stretched in three stages using five pairs of Nelson type rolls, then subjected to a relaxation heat treatment with 3% relaxation, and then wound up.

The stretching conditions were a take-up roll temperature of 60°C, a first stretching roll temperature of 120°C, a second stretching roll temperature of 150°C, a third stretching roll temperature of 160°C, and a tension adjustment roll after stretching that was not heated. The first stage stretching ratio was 60% of the total stretching ratio, and the remainder was divided into two stages for stretching. The spinning speed is 100
The yarn was spun at 0 m/min, and the fineness of the drawn yarn was approximately 840 denier.

In Comparative Example 1, the amount of colorant (carbon black) added to the polyester did not satisfy the constituent requirements of the present invention.
Furthermore, in Comparative Example 2, the ratio of the core component to the sheath component does not satisfy the constituent requirements of the present invention.

Comparative Examples 3 and 4 are commercially available black dope-dyed polyester fibers and nylon 6 fibers used for fishing nets.

7-18 The amine decomposition resistance of each fiber obtained in Example 1.2 and Comparative Examples 1 to 4 was evaluated at 135°C in ammonia gas.
The strength retention rate after 5 hours of treatment was evaluated, and the results are also listed in the table.

Next, each of the fibers obtained in Example 1.2 and Comparative Examples 1 to 4 was twisted so that the twist coefficient was 3000 at the time of pre-twisting, and the two pre-twisted yarns were combined to obtain the number of first twists , 6, and the net yarn was made with the same number of twists as the knotless net, and heat set at 180° C. for 1 minute at a constant length. The impact strength, stiffness, and durability of this net yarn were evaluated and are also listed in the table.

The impact test was performed using a high-speed tensile tester manufactured by Shimadzu Corporation at a test length of 25 cm and a tensile speed of 5 m/sec.

In addition, the mesh was attached to the chuck of the aforementioned tensile tester with an inner diameter of 10 mm.
A 3 cm metal ring was attached to the sample, and the resistance was measured when the ring was pulled out. The drawing speed was 30 cm/min, and a larger value indicates stiffness.

Durability was tested using an underwater fatigue tester manufactured by Shimadzu Corporation.
The figure shows the number of times the sample is cut at a rate of 1 time/second when the load is 14.4 kg and the operation is 0 kg.

In addition, the "color tone" and "gloss" of this mesh yarn were judged with the naked eye, and the results are also listed in the table. ◎ indicates extremely good, 0 indicates good, and △ indicates there is a problem.

(The following is a blank space) As is clear from the results in the table, the composite fibers that satisfy the constituent requirements of the present invention have extremely good amine decomposition resistance equivalent to Nanlon 6.

As is clear from the results in the table, the composite fibers satisfying the constituent requirements of the present invention have extremely good impact strength and stiffness equivalent to polyester, and have extremely good durability equivalent to nylon 6.

As is clear from the results in the table, the spun-dyed yarn for fishing nets made of composite fibers satisfying the constituent requirements of the present invention is close to commercially available spun-dyed yarn and is good.

As is clear from the results in the table, the dyed yarn for fishing nets made of composite fibers that satisfies the constituent requirements of the present invention has excellent amine decomposition resistance, high modulus and specific gravity, and good color tone and gloss. In addition, the fishing net obtained by knitting the dyed yarn for fishing net has good sedimentation properties, and the net sways less in the sea.
Moreover, it had excellent durability.

〔Effect of the invention〕

The dyed yarn for fishing nets according to the present invention has a modulus equal to or higher than that of conventional polyester fibers, and has excellent amine decomposition resistance and durability equivalent to that of polyamide fibers, and is superior to conventional polyester fibers. , and has excellent properties that could not be achieved with spun-dyed yarn for fishing nets using polyamide fibers.

Furthermore, compared to conventional spun-dyed yarns, it is possible to reduce the amount of colorant added, which is advantageous in terms of cost.

In addition, the fishing net according to the present invention has high specific gravity and high modulus by using the above-mentioned dyed yarn for fishing nets, so it has characteristics such as excellent settling properties and less net shaking in the sea, It also has excellent amine decomposition resistance. Therefore, it is possible to provide a fishing net that has excellent fishing performance and operability, and can withstand long-term use.

Claims (4)

[Claims] (1) A spun-dyed yarn for fishing nets and fishing nets made of composite fibers, wherein the composite fibers are core-sheath type composite fibers having a core component of polyester containing ethylene terephthalate as a main component and a sheath component of polyamide, and The proportion of the polyester core component is 30 to 90% by weight, the polyester core component contains 0.1 to 5.0% by weight of the colorant based on the polyester, and the intrinsic viscosity of the polyester core component [η
] is 0.8 or more, birefringence is 160 x 10^-^3 ~ 19
0x10^-^3, the density is 1.380g/cm^3 or more, and the sulfuric acid relative viscosity [ηr] of the polyamide sheath component is 2
．． 8 or more, birefringence is 45 x 10^-^3 or more, density is 1
．． A spun-dyed yarn for fishing nets, characterized by being made of a composite fiber having a weight of 135 g/cm^3 or more. (2) The dyed yarn for fishing nets according to claim (1) has a strength of 5.5 g/d or more, an elongation of 20% or more, an initial tensile resistance of 60 g/d or more, and a density of 1. 200g/cm
^3 or more, dry heat shrinkage rate is 7% or more, wet knot strength is 4.5
A spun-dyed yarn for fishing nets, characterized in that it has a g/d or higher. (3) A fishing net characterized by using the dyed yarn for fishing nets according to claim (1). (4) A fishing net characterized by using the dyed yarn for fishing nets according to claim (2).